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US5998631A - Cyclic phenol sulfide having at least one sulfinyl or sulfonyl group and process for producing the same - Google Patents

Cyclic phenol sulfide having at least one sulfinyl or sulfonyl group and process for producing the same Download PDF

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US5998631A
US5998631A US09/068,583 US6858398A US5998631A US 5998631 A US5998631 A US 5998631A US 6858398 A US6858398 A US 6858398A US 5998631 A US5998631 A US 5998631A
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hydrocarbon group
cyclic phenol
sulfinyl
hydrogen atom
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Hitoshi Kumagai
Setsuko Miyanari
Sotaro Miyano
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Cosmo Oil Co Ltd
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Cosmo Oil Co Ltd
Cosmo Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms

Definitions

  • the present invention relates to a novel cyclic phenol sulfide having at least one sulfinyl or sulfonyl group which can be used as, e.g., a metal-trapping agent, an ion sensor, a sensor with substrate specificity, a separating-membrane material, a polymer material, an oxidizing catalyst, a phase-transfer catalyst, a synthetic enzyme, a light energy converter, or an intermediate for functional molecules using a recognition ability of an ion or molecule, and a process for producing the same.
  • a metal-trapping agent e.g., an ion sensor, a sensor with substrate specificity, a separating-membrane material, a polymer material, an oxidizing catalyst, a phase-transfer catalyst, a synthetic enzyme, a light energy converter, or an intermediate for functional molecules using a recognition ability of an ion or molecule, and a process for producing the same.
  • Alkylphenol sulfides are conventionally known as an antioxidant (e.g., U.S. Pat. Nos. 2,239,534, 3,377,334), a rubber sulfurizer (e.g., U.S. Pat. Nos. 3,468,961, 3,647,885), a polymer stabilizer (e.g., U.S. Pat. Nos. 3,882,082, 3,845,013, 3,843,600), an anticorrosive (e.g., U.S. Pat. No. 3,684,587), and a starting material for phenates for use as a lubricating-oil additive (Hori et al., Sekiyu Gakkai-shi, Vol. 34, p. 446, 1991).
  • an antioxidant e.g., U.S. Pat. Nos. 2,239,534, 3,377,33
  • a rubber sulfurizer e.g., U.S. Pat. Nos. 3,468,961, 3,647,885
  • Known processes for producing conventional phenol sulfides include a method in which a phenol and elemental sulfur are used as starting materials (e.g., A. J. Neale et al., Tetrahedron, Vol. 25, p. 4593, 1969); a method in which a phenol, elemental sulfur, and a base catalyst are used as starting materials (e.g., U.S. Pat. No. 3,468,961); a method in which a phenol, elemental sulfur, and a molecular halogen are used as starting materials (e.g., B. Hortling et al., Polym. Bull., Vol.
  • An object of the present invention is to provide a novel cyclic phenol sulfide having at least one sulfinyl or sulfonyl group and a process for producing the same.
  • X represents a hydrogen atom, a hydrocarbon group, or an acyl group
  • Y represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, --COR 1 , --OR 2 , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 , in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represents a hydrogen atom or a hydrocarbon group; and n represents an integer of 4 to 12, provided that the plural
  • the present invention provides a cyclic phenol sulfide having at least one sulfinyl or sulfonyl group represented by formula (1): ##STR3## wherein X represents a hydrogen atom, a hydrocarbon group, or an acyl group; Y represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, --COR 1 , --OR 2 , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 , in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represents a hydrogen atom or a hydrocarbon group; Z represents one member selected from the group consisting of S, a sulfinyl group, and a sulfonyl group; and n represents an integer of 4 to 12, provided that the plural X'
  • X represents a hydrogen atom, a hydrocarbon group, or an acyl group.
  • the carbon atom number of the hydrocarbon group represented by X is not particularly limited as long as the number is 1 or more. Preferably, the carbon atom number of the hydrocarbon group is from 1 to 50.
  • the hydrocarbon group include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alicyclic-aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic-aliphatic hydrocarbon group.
  • Preferred examples of the saturated aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n-hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, 1-methyloctyl, ethylheptyl, n-decyl, 1-methylnonyl, n-undecyl, 1,1-dimethyln
  • Preferred examples of the unsaturated aliphatic hydrocarbon group include alkenyl and alkynyl groups such as vinyl, allyl, isopropenyl, 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl, and decenyl groups; and a hydrocarbon group derived from a polymer or copolymer of acetylene, butadiene, or isoprene.
  • alkenyl and alkynyl groups such as vinyl, allyl, isopropenyl, 2-butenyl, 2-methylallyl, 1,1-dimethylallyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 4-pentenyl, hexenyl, octenyl, nonenyl, and decenyl groups
  • Preferred examples of the alicyclic hydrocarbon group include cycloalkyl, cycloalkenyl, and cycloalkynyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 2-methylcyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, 4-methylcyclohexenyl, and 4-ethylcyclohexenyl groups.
  • Preferred examples of the alicyclic-aliphatic hydrocarbon group include cycloalkyl-, cycloalkenyl-, or cycloalkynyl-substituted alkyl, alkenyl, and alkynyl groups such as cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, cycloheptylmethyl, cyclooctylethyl, 3-methylcyclohexylpropyl, 4-methylcyclohexylethyl, 4-ethylcyclohexylethyl, 2-methylcyclooctylethyl, cyclopropenylbutyl, cyclobutenylethyl, cyclopentenylethyl, cyclohexenylmethyl, cycloheptenylmethyl, cyclooctenylethyl,
  • Preferred examples of the aromatic hydrocarbon group include an aryl group such as phenyl and naphthyl groups; and alkylaryl, alkenylaryl, and alkynylaryl groups such as 4-methylphenyl, 3,4-dimethylphenyl, 3,4,5-trimethylphenyl, 2-ethylphenyl, n-butylphenyl, tert-butylphenyl, amylphenyl, hexylphenyl, nonylphenyl, 2-tert-butyl-5-methylphenyl, cyclohexylphenyl, cresyl, oxyethylcresyl, 2-methoxy-4-tert-butylphenyl, and dodecylphenyl.
  • the alkyl moiety of the alkylaryl group, the alkenyl moiety of the alkenylaryl group, and the alkynyl moiety of the alkynylaryl group may have a cyclic structure
  • Preferred examples of the aromatic-aliphatic hydrocarbon group include aralkyl, aralkenyl, and aralkynyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 1-(4-methylphenyl)ethyl, 2-(4-methylphenyl)ethyl, 2-methylbenzyl, and 1,1-dimethyl-2-phenylethyl groups.
  • the alkyl moiety of the aralkyl group, the alkenyl moiety of the aralkenyl group, and the alkynyl moiety of the aralkynyl group may have a cyclic structure.
  • the carbon atom number of the acyl group is not particularly limited as long as the number is 1 or more.
  • the carbon atom number of the acyl group is from 1 to 40.
  • Preferred examples of the acyl group include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, succinyl, pivaloyl, stearoyl, benzoyl, phenylpropionyl, toluoyl, naphthoyl, phthaloyl, indancarbonyl, p-methylbenzoyl, and cyclohexylcarbonyl groups.
  • Y represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, --COR 1 , --OR , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 .
  • hydrocarbon group and the --COR 1 group both represented by Y include the same hydrocarbon groups and acyl groups as those enumerated hereinabove with regard to X. Preferred examples thereof also include the same preferred groups.
  • halogenated hydrocarbon group examples include halogenated hydrocarbon groups formed by halogen-substituting the same hydrocarbon groups as those enumerated hereinabove with regard to X. Preferred examples thereof also include halogenated hydrocarbon groups derived from the same preferred hydrocarbon groups.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represents a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include the same hydrocarbon groups as those enumerated hereinabove with regard to X, and preferred examples thereof also include the same preferred groups.
  • the above hydrocarbon group may be substituted with at least one substituent such as --COR 1 , --OR 2 , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 .
  • substituents such as --COR 1 , --OR 2 , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 .
  • the halogen atom may be any of fluorine, chlorine, bromine, and iodine atoms.
  • These substituents may be of one kind or two or more kinds.
  • the number of the substituents may be one or more per hydrocarbon group.
  • the number of X's present is from 4 to 12 per molecule.
  • the plural X's are the same or different.
  • the number of Y's present is from 4 to 12 per molecule.
  • the plural Y's are the same or different.
  • the number of Z's present is from 4 to 12 per molecule, and at least one of the plural Z's is a sulfinyl group or a sulfonyl group.
  • the cyclic phenol sulfide containing at least one sulfinyl or sulfonyl group according to the present invention can be produced by oxidizing a sulfide bond in a cyclic phenol sulfide represented by formula (2), wherein X represents a hydrogen atom, a hydrocarbon group, or an acyl group; Y represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, --COR 1 , --OR 2 , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 , in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represents a hydrogen atom or a hydrocarbon group; and n represents an integer of 4 to 12, provided that the plural X's or the plural Y's are the same or different.
  • X represents a hydrogen atom, a hydrocarbon group, or an acyl group, and examples thereof are the same as those for the X in formula (1) described above.
  • Y represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, --COR 1 , --OR 2 , --COOR 3 , --CN, --CONH 2 , --NO 2 , --NR 4 R 5 , a halogen atom, --SO 4 R 6 , or --SO 3 R 7 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each represents a hydrogen atom or a hydrocarbon group. Examples thereof are the same as those for the Y in formula (1) described above.
  • the number of X's present is from 4 to 12 per molecule.
  • the plural X's are the same or different.
  • the number of Y's present is from 4 to 12 per molecule.
  • the plural Y's are the same or different.
  • a preferred process for producing a cyclic phenol sulfide represented by formula (2) comprises first reacting a phenol compound represented by formula (3): ##STR4## wherein Y represents a hydrogen atom or a hydrocarbon group, which is unsubstituted phenol or has a hydrocarbon group in the 4-position of the benzene ring to the hydroxyl group, with an appropriate amount of elemental sulfur in the presence of an appropriate amount of at least one metallic reagent selected from alkali metal reagents and alkaline earth metal reagents.
  • the phenol compound and elemental sulfur used as starting materials are fed in such a proportion that the amount of the elemental sulfur is at least 0.1 gram equivalent, preferably at least 0.35 gram equivalents, per gram equivalent of the phenol compound.
  • the amount of the elemental sulfur fed as a raw material is preferably up to 20 gram equivalents, especially preferably up to 10 gram equivalents, per gram equivalent of the phenol compound.
  • alkali metal reagents include elemental alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal carbonates, alkali metal alkoxides, and alkali metal halides.
  • alkaline earth metal reagents include elemental alkaline earth metals, alkaline earth metal hydrides, alkaline earth metal hydroxides, alkaline earth metal oxides, alkaline earth metal carbonates, alkaline earth metal alkoxides, and alkaline earth metal halides.
  • the use amount of the alkali metal reagent or alkaline earth metal reagent is at least 0.005 gram equivalents, preferably at least 0.01 gram equivalent, per gram equivalent of the phenol compound. Although there is no particular upper limit on the use amount of the alkali metal reagent or alkaline earth metal reagent, the amount thereof is preferably less than 10 gram equivalents, especially preferably less than 5 gram equivalents.
  • the hydrogen atom of the hydroxyl group can be suitably converted, if desired, to a hydrocarbon group or acyl group by etherification, acylation, or the like. If Y is a hydrogen atom, the hydrogen atom is directly replaced with a substituent. If Y is an alkyl group, a dealkylation reaction is conducted, followed by conversion of the substituent. Thus, a cyclic phenol sulfide represented by formula (2) can be produced.
  • Methods for the replacement of a substituent include a method in which a cyclic phenol sulfide represented by formula (2) described above in which Y is an alkyl group is dealkylated with an aluminum chloride or cobalt oxide catalyst or the like to convert each alkyl group to hydrogen. or cobalt oxide catalyst or the like to convert each alkyl group to hydrogen.
  • Another method for replacement of a substituent comprises causing an appropriate nitrating agent, e.g., nitronium tetrafluoroborate or nitric acid, to act on the dealkylated cyclic phenol sulfide to convert the hydrogen atoms introduced by the dealkylation to nitro groups.
  • an appropriate nitrating agent e.g., nitronium tetrafluoroborate or nitric acid
  • the nitro groups can be converted to amino groups by reduction with an appropriate reducing agent, e.g., iron/hydrochloric acid.
  • an appropriate reducing agent e.g., iron/hydrochloric acid.
  • diazotize the resultant compound with sodium nitrate or the like and cause an appropriate halogenating agent, e.g., copper chloride, a cyano-introducing agent, or water to act on the diazotization product in the presence of hydrochloric acid or the like to convert the diazo groups to halogen atoms, cyano groups, or hydroxyl groups, respectively.
  • the hydroxyl groups can be converted to acid sulfuric ester groups by the reaction of a sulfuric ester-forming agent, e.g., sulfuric acid.
  • a sulfuric ester-forming agent e.g., sulfuric acid
  • the hydroxyl groups can also be converted to alkyl ether groups by forming an alkali metal phenoxide, e.g., sodium phenoxide, and causing an alkyl halide to act thereon.
  • hydrogen atoms introduced by the dealkylation can be converted to sulfo groups.
  • the cyclic phenol sulfide represented by formula (2) thus synthesized can be converted to a cyclic phenol sulfide containing at least one sulfinyl or sulfonyl group by oxidizing the sulfide bond thereof.
  • a general oxidizing agent can be used to conduct the oxidation reaction of sulfide bonds.
  • oxidizing agents include hydrogen peroxide, organic peroxides, peracids, halogen oxides, N-halogenated imido compounds, molecular halogens, oxygen, ozone, nitric acid, inorganic oxides, and the like.
  • Preferred oxidizing agents include hydrogen peroxide, molecular halogens, and inorganic oxides.
  • organic peroxides include t-butyl peracetate, perbenzoic acid, m-chloroperbenzoic acid, and benzoyl peroxide.
  • Preferred examples of the peracids include peracetic acid, trifluoroperacetic acid, and bis(trimethylsilyl) peroxide.
  • halogen oxides include sodium periodate, sodium hypochiorite, sodium bromite, and iodobenzenes.
  • N-halogenated imido compounds include N-bromosuccinimide and N-chlorosuccinimide.
  • Examples of the molecular halogens include chlorine, bromine, and iodine. Especially preferred is bromine.
  • inorganic oxides include manganese (IV) oxide, cerium (IV) oxide, ruthenium (IV) oxide, chromium (IV) oxide, lead (IV) tetraacetate, sodium perborate, and permanganic acid salts. Especially preferred is sodium perborate.
  • oxidizing agents may be used alone or in combination of two or more thereof.
  • the oxidation number for sulfur can be changed by changing the amount by equivalent of the oxidizing agent added based on the amount of the sulfide bonds of the cyclic phenol sulfide represented by formula (2).
  • sulfinyl bonds are apt to generate when the oxidizing agent is added in an amount nearly equivalent to the sulfide bonds, usually from 1.0 to 1.5 gram equivalents, preferably from 1.0 to 1.2 gram equivalents, per gram equivalent of the sulfide bonds.
  • sulfonyl bonds are apt to generate when the oxidizing agent is used in excess, usually in an amount of from 2 to 10 gram equivalents, preferably from 2 to 6 gram equivalents, per gram equivalent of the sulfide bonds.
  • a catalyst may be used for the reaction if necessary.
  • Preferred examples of the catalyst of using, for example, hydrogen peroxide as an oxidizing agent include vanadium (V) oxide, sodium metavanadate (V), titanium trichloride, tungsten (VI) oxide, and sodium phosphate. These catalysts may be used alone or in combination of two or more thereof.
  • the use amount of the catalyst is not particularly limited, it is generally from 0.005 to 10 gram equivalents, preferably from 0.01 to 6 gram equivalents, per gram equivalent of the sulfide bond.
  • the oxidation reaction can also be conducted using electrochemical and photochemical techniques. Furthermore, an enzyme can be used to conduct the oxidation.
  • solvent to be used examples include chlorinated solvents such as chloroform and dichloromethane, alcohols such as methanol and ethanol, and protonic solvents such as acetonitrile, acetic acid, and water.
  • chlorinated solvents such as chloroform and dichloromethane
  • alcohols such as methanol and ethanol
  • protonic solvents such as acetonitrile, acetic acid, and water.
  • An alcohol solvent e.g., methanol, ethanol, or butanol, or a chlorinated solvent, e.g., chloroform or dichloromethane
  • hydrogen peroxide or an organic oxide is used as an oxidizing agent
  • a solvent such as water, acetonitrile, or trifluoroacetic acid is preferred if a peracid is used as an oxidizing agent
  • a solvent such as methanol/water, acetone, or dioxane is preferred if a halogen oxide is used as an oxidizing agent
  • an alcohol solvent e.g., methanol, is preferred if an N-halogenated compound is used as an oxidizing agent
  • a two-phase system consisting of a chlorinated solvent, e.g., chloroform or dichloromethane, and a weakly alkaline aqueous solution, e.g., an aqueous solution of a hydrogen carbonate, is preferred if a mo
  • nitric acid is used as an oxidizing agent; on the other hand, dichloromethane is preferred if ozone for the oxidation is used.
  • dichloromethane is preferred if an inorganic oxide is used, it is preferred to use pyridine, acetonitrile, acetic acid, a hydrocarbon, a chlorinated solvent, e.g., dichloromethane or chloroform, or a solvent consisting of a mixture thereof.
  • a solvent such as acetonitrile or acetic acid is preferably used.
  • a chlorinated solvent e.g., chloroform or dichloromethane, or methanol is preferably used. These solvents may be used alone or in combination of two or more thereof.
  • the use amount of the solvent is not particularly limited, it may be generally from 5 to 100 ml, preferably from 10 to 50 ml, per g of the cyclic phenol sulfide.
  • Reaction temperatures are preferably from -78° C. to 100° C.
  • the preferred temperatures vary depending on the oxidizing agents used. Specifically, temperatures of from 15° C. to 65° C. are preferred if hydrogen peroxide, oxygen, nitric acid, or an inorganic oxide is used as an oxidizing agent; temperatures of from -10° C. to 90° C. are preferred if an organic peroxide or a peracid is used as an oxidizing agent; and temperatures of from -10° C. to 30° C. are preferred if a molecular halogen or a halogen oxide is used.
  • ozone for the oxidation the reaction is preferably conducted at -78° C. In the case where an electrochemical technique or a photochemical technique is used for the oxidation, the reaction is preferably conducted at a temperature of from 20° C. to 60° C.
  • the period of this reaction is not particularly limited, and an appropriate reaction period may be used according to the kind and incorporation amount of the oxidizing agent. In general, a reaction period of from 0.5 to 120 hours may be used.
  • reaction product comprising a mixture of oxidative derivatives differing in oxidation number
  • these derivatives may be separated by an ordinary separation technique, e.g., recrystallization.
  • reaction product (I) was obtained as colorless crystals.
  • the resultant suspension was cooled in a water bath, and 0.03 ml of bromine was gradually added thereto dropwise. The suspension was further stirred for 3 hours in a water bath.
  • the reaction mixture obtained was separated into an aqueous layer and an organic layer.
  • the aqueous layer was extracted with dichloromethane (20 ml ⁇ 2), and the resultant dichloromethane solution was added to the organic layer obtained above.
  • This mixture was sufficiently washed with saturated aqueous common-salt solution and then dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off to obtain 1.02 g of a cream-colored powder.
  • This powder was treated with silica gel column chromatography (dichloromethane) to separate 244 mg of a reaction product (IV) and by-products from the starting materials remaining unreacted.
  • the sodium ion concentration in the aqueous solution of the sample containing cyclic phenol sulfide (II) after the extraction was found to be lower by 38% than that in the aqueous solution of the sample not containing cyclic phenol sulfide (II) after the test.
  • the sodium ion concentration in the aqueous solution of the sample containing cyclic phenol sulfide (III) after the test was found to be lower by 58% than that in the aqueous solution of the sample not containing cyclic phenol sulfide (III) after the extraction.
  • the cyclic phenol sulfide of the present invention is an entirely novel compound comprising phenol frameworks linked to each other with sulfide, sulfoxide, or sulfone bonds. It is useful, for example, as an antioxidant, a catalyst, a metal-trapping agent, a light sensor, an ion sensor, a sensor with substrate specificity, a separating-membrane material, a polymer material, a phase-transfer catalyst, an artificial enzyme, a light energy converter, or as an intermediate for functional molecules using a recognition ability of an ion or molecule.

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PCT/JP1997/002789 WO1998009959A1 (fr) 1996-09-06 1997-08-08 Sulfure de phenol cyclique contenant un groupe sulfinyl ou sulfonyl et procede de preparation correspondant

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US20030060637A1 (en) * 2000-03-13 2003-03-27 Sotaro Miyano Cyclic aniline sulfide and process for preparing the same
US6602970B2 (en) 2000-06-13 2003-08-05 Toagosei Co., Ltd. 2-cyanoacrylate composition
US20050045648A1 (en) * 2003-08-28 2005-03-03 Tom Mayrose Container holder and a system for supporting containers and a method for holding containers
US20090042120A1 (en) * 2006-04-13 2009-02-12 Hodogaya Chemical Co., Ltd. Oxidized mixed cyclic phenol sulfides, and charge control agents and toners using the same
US20090275783A1 (en) * 2007-01-16 2009-11-05 Hodogaya Chemical Co., Ltd. Methods for producing oxidized cyclic phenol sulfides
US20110028737A1 (en) * 2008-02-14 2011-02-03 Hodogaya Chemical Co., Ltd. Method for continuously producing oxidized cyclic phenol sulfides
US20110045396A1 (en) * 2008-05-09 2011-02-24 Hodogaya Chemical Co., Ltd. Charge Controlling Agent and Toner Using Metal Compound of Cyclic Phenol Sulfide

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DE69822503T2 (de) * 1997-12-09 2005-01-20 Cosmo Oil Co. Ltd. Sulfonierte derivate zyklischer phenolsulfide, verfahren zu ihrer herstellung, mittel zur trennung und gewinnung, die zyklische phenolsulfide enthalten, auf diesen basierende methoden zur trennung ung gewinnung und medikamentzusammensetzungen, die diese sulfide enthalten
JP2000191658A (ja) * 1998-10-22 2000-07-11 Cosmo Research Inst 環状フェノ―ル硫化物金属錯体、それからなる触媒及び過酸化水素の分析方法
JP4480245B2 (ja) * 2000-03-13 2010-06-16 株式会社コスモ総合研究所 環状アニリン硫化物とその製造方法
CN101589344B (zh) 2007-01-25 2012-07-25 保土谷化学工业株式会社 电子照相用感光体
CN101440084B (zh) * 2008-12-29 2012-10-03 山东师范大学 一种砜杂杯[4]芳烃化合物及其微波辅助合成方法
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JPWO2012036171A1 (ja) 2010-09-15 2014-02-03 保土谷化学工業株式会社 電荷制御剤及びそれを用いたトナー

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